Rubber stabilized with phenylene-diamine-s-triazines

ABSTRACT

THERE ARE PREPARED 1,3,5-TRIAZINES OF THE FORMULA:   2-(Z-NH-1,4-PHENYLENE-NH-),4-X,6-Y-S-TRIAZINE   WHERE X AND Y ARE SR1 WHERE R1 IS ALKYL OF 1 TO 12 CARBON ATOMS OR ARYL, CN, OR2 WHERE R2 IS HYDROGEN, ALKYL OF 1 TO 12 CARBON ATOMS, ARYL, ALLYL OR METHALLYL, PHENYL P-PHENYLENEDIAMINO,   -N(-R3)-R4   THE COMPOUNDS ARE USEFUL TO STABILIZE VULCANIZED AND VULCANIZABLE NATURAL AND SYNTHETIC RUBBER COMPOSITIONS.   4-X,6-Y-S-TRIAZIN-2-YL   WHERE R7 IS ALKYL OF 1 TO 18 CARBON ATOMS, BENZYL OR PHENYL OR THE GROUP   -CO-R7   WHERE R3 AND R4 ARE HYDROGEN, ALKYL OF 1 TO 18 CARBON ATOMS, ALKYL, OF 1 TO 18 CARBON ATOMS SUBSTITUTED WITH -OH, -CN OR OR5 WHERE R5 IS ALKYL OF 1 TO 18 CARBON ATOMS, ALLYL, METHYLLYL, CYCLOALKYL OF 5 TO 8 CARBON ATOMS, ARYL OR BENZYL, ONE OF R3 AND R4 IS ALPHA OR BETA NAPHTHYL AND THE OTHER IS HYDROGEN, R3 AND R4 TOGETHER WITH THE NITROGEN ATOM FORM A 5 TO 8 MEMBERED RENG WHICH HAS FROM 4 TO 7 -CH2- GROUPS OF WHICH 0 OR 1 HYDROGEN ATOM IS OR OF WHICH 2 HYDROGEN ATOMS ATTACHED TO DIFFERENT CARBON ATOMS ARE SUBSTITUTED BY LOWER ALKYL, R3 AND R4 TOGETHER WITH THE NITROGEN ATOM FORM A 5 TO 8 MEMBERED RING WHICH HAS FROM 3 TO 6 -CH2- GROUPS OF WHICH 0 OR 1 HYDROGEN ATOMS IS OR OF WHICH 2 HYDROGEN ATOMS ATTACHED TO DIFFERENT ATOMS IS OR OF WHICH 2 HYDROGEN ATOMS LOWER ALKYL AND SAID RING HAS ONE HETERO OXYGEN OR SULFUR ATOM OR NR6 WHERE R6 IS HYDROGEN OR LOWER ALKYL, OR X IS CHLORINE, Z IS HYDROGEN, ALKYL OF 1 TO 8 CARBON ATOMS, CYCLOALKYL OF 5 TO 8 CARBON ATOMS, PHENYL, BENZYL, ACYL OF THE FORMULA

United States Patent Ofiice 3,828,002 RUBBER STABILIZED WITH PHENYLENE- DIAMINE-S-TRIAZINES Hermann Westlinning, Kleinostheim, Werner Schwarze,

Frankfurt, and Horst Fleischhauer, Grossauheim, Germany, assiguors to Deutsche Goldund Silber-Scheideanstalt vormals Roessler, Frankfurt am Main, Germany No Drawing. Filed Dec. 19, 1972, Ser. No. 316,565 Claims priority, application Germany, Dec. 27, 1971, P 21 64 800.0 Int. Cl. C08c 11/52 US. Cl. 260-453 N 27 Claims ABSTRACT OF THE DISCLOSURE There are prepared 1,3,5-triazines of the formula:

where X and Y are SR where R, is alkyl of 1 to 12 carbon atoms or aryl, CN, R where R is hydrogen, alkyl of 1 to 12 carbon atoms, aryl, allyl or methallyl, phenyl p-phenylenediamino,

where R and R are hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of l to 18 carbon atoms substituted with -OH, CN or 0R where R is alkyl of 1 to 18 carbon atoms, allyl, methallyl, cycloalkyl of 5 to 8 carbon atoms, aryl or benzyl, one of R and R is alpha or beta naphthyl and the other is hydrogen, R and R together with the nitrogen atom form a 5 to 8 membered ring which has from 4 to 7 -CH groups of which 0 or 1 hydrogen atom is or of which 2 hydrogen atoms attached to difierent carbon atoms are substituted by lower alkyl, R and R together with the nitrogen atom form a 5 to 8 membered ring which has from 3 to 6 -CI-I groups of which 0 or 1 hydrogen atoms is or of which 2 hydrogen atoms attached to different carbon atoms are substituted by lower alkyl and said ring has one hetero oxygen or sulfur atom or NR where R is hydrogen or lower alkyl, or X is chlorine, Z is hydrogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl, benzyl, acyl of the formula where R, is alkyl of 1 to 18 carbon atoms, benzyl or phenyl or the group The compounds are useful to stabilize vulcanized and vulcanizable natural and synthetic rubber compositions.

The invention is directed to new 1,3,5-triazine compounds which have the phenylenediamine group or phenylenediamine derivatives as ligands and their industrial uses, especially as stabilizers for rubber containing products.

Patented Aug. 6, 1974 -It' is known that rubber vulcanizates with increasing life undergo structural change which leads to a reduction of its useful value. The cause of this change is the influence of oxygen, ozone, light and heat, individually or in combination. If there is simultaneously present a dynamic stress of the rubber vulcanizate then the influence of these factors is increased. In order to stabilize the rubber against these quality reducing influences, there are known a whole series of materials which are included under the name ageing inhibitors or fatigue inhibitors. Many of the customary ageing inhibitors do not serve as fatigue inhibitors, especially those which are non-staining.

Known anti-ageing agents for rubber products are secondary aromatic amines such as N-phenyl-aor -[3-naphthylamine or substituted p-phenylene-diamine as perhaps N-cyclohexyl-N'-phenyl-p-phenylenediamine or N-isopropyl-N'-phenyl-p-phenylene-diamine; additional anti-agers are N-(1,3-dimethylbutyl) N phenyl-p-phenylenediamine, N,N di-l,4-dimethylpentyl-p-phenylenediamine, N,N'-di-1-methylheptyl p phenylenediamine, N,N'-diphenyl-p-phenylenediamine, di-fi-naphthyl-pphenylenediamine, -2,2,4-trimethyl 1,2 dihydro-6-ethoxy quinoline, 6-dodecyl-2-,2,4-trimethyl-1,2-dihydro quinoline, poly-2,2, 4-trimethyl 1,2 dihydroquinoline, 4,4'-thiobis-(2-tert. butyl-5-methylphenol), 4,4'-butylidene-bis-(2-tert. butyl- S-methylphenol), 2,2 methylene bis(4-methyl-6-tert. butylphenol), 2,6-di-tert.butyl-p-cresol, 4,4-dihydroxydiphenyl, Z-mercapto-benzimidazole, the zinc salt of 2- mercapto-benzimidazole and ozone protective Wax. There are also used as anti-aging agents diphenylamine derivatives, mixtures of aralkylated phenols, mixtures of alkyl and aralkyl substituted phenols, benzofurane derivatives, steric hindered bisphenols as well as certain condensation products from aldol and a-naphthylamine, reaction product of acetone and diphenylamine and the reaction product of 6-tert. butyl-m-creso and SCl Sometimes these materials are used in mixtures with each other.

The p-phenylenediamine derivatives protect the rubber products against the eifectst of ozone and against fatigue. However, they have the important disadvantage that they are not resistant to light and hence they lead to the discoloration of rubber. This disadvantage is strongly evident in light colored or white rubber products. In carbon black filled products this discoloration is masked but the discolorations of materials such as, for example, lacquers, films or light colored synthetic resins, including elastomers, in contact with the rubber products are not prevented thereby. Such contact discolorations are especially known and feared in the automotive industry.

There have already been proposed numerous derivatives of 1,3,5-triazines for various use. These triazines, for example, have in the 2-, 4- and/or in the 6-position halogen atoms as well as sulfur and/or nitrogen containing ligands; they have also been proposed, among others, for use in the stabilization of organic materials, as for example, polymers (U.S. Pats. to Dexter 3,240,749, Dexter 3,245,992, Dexter 3,257,354, Pines 3,418,272 and Biland 3,530,127, British Patent 977,589 and French Patent 675,785, etc.). In Dexter Patent 3,257,354, for example, there is disclosed that natural rubber or synthetic rubber, as for example, cis-polyisoprene or styrene-butadiene rubber can be protected against oxidative decomposition by triazine compounds which have free OH- containing phenyl groups. The activity of these products is obviously tied to the presence of free phenol groups.

There is also a series of different triazine derivatives which can be used in special manner for the protection of organic materials against ultraviolet rays (see German Auslegeschrifts 1,240,083 and 1,241,452). These compounds also contain phenyl substituents with attached free OH groups.

In the above cited French patent there is a shotgun disclosure of an extremely large number of derivatives of s-triazines with many ligands which are not specifically defined or definable. These ligands can be bound to the triazine ring either directly or by way of the hetero atoms oxygen, nitrogen or sulfur. Among the derivable triazine derivatives there are found very many which do not have any anti-aging effect in rubber vulcanizates. Even in the three specific examples triazines are named which, as is evident from the test values recited, give practically no protection in the vulcanizates against ageing. Also in the French patent, there is disclosed no rule which shows which of the numerous and very different triazines derivatives either are or could be effective anti-ageing agents.

From the extraordinarily large number of known triazine derivatives a choice has now been found and surprisingly derivatives of 1,3,5-triazines found which unforeseeably produce valuable and industrially outstanding properties in rubber vulcanizates.

There are prepared 1,3,5-triazines of the formula:

where X and Y are the same or different and are (A) SR where R is alkyl of l to 12 carbon atoms or aryl, (B) ON, (C) R where R is hydrogen, alkyl. of l to 12 carbon atoms, aryl, allyl or methallyl, (D) phenyl p-phenylenediamino of the formula where R and R are (a) hydrogen, (b) alkyl of l to 18 carbon atoms, (c) alkyl of l to 18 carbon atoms substituted with OH, CN or 0R where R is alkyl of l to 18 carbon atoms, (d) allyl, (e) methallyl, (f) cycloalkyl of 5 to 8 carbon atoms, (g) aryl or (h) benzyl, (i) one of R and R is alpha or beta naphthyl and the other is hydrogen, (R) R and R together with the nitrogen atom from a 5 to 8 membered preferably a 5 or 6 membered ring which has I from 4 to 7 preferably 4 or 5CH groups of which 0 or 1 hydrogen atom is or of which 2 hydrogen atoms attached to different carbon atoms are substituted by lower alkyl, (1) R and R together with the nitrogen atom form a 5 to 8 membered preferably a 5 or 6 membered ring which has from 3 to 6 preferably 3 or 4 CI-I groups of which 0 or 1 hydrogen atom is or of which 2 hydrogen atoms attached to different carbon atoms are substituted by lower alkyl and said ring has one hetero oxygen or sulfur atom or NR where R is hydrogen or lower alkyl, or X is chlorine, Z is hydrogen, alkyl of l to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl, benzyl,. acyl of the formula where R is alkyl of 1 to 18 carbon atoms, benzyl or phenyl or the group All of the named alkyl groups can be straight or branched chain.

In the case of substituted alkyl groups they are preferably monoor di-substituted, especially monosubstituted. Aryl in the definition for X and Y is especially phenyl, which in a given case is substituted by lower alkyl or methoxy groups. Lower alkyl groups are those containing 1 to 5 carbon atoms. Preferably the radicals X and Y of the group of formula II are the same as the radicals X and Y of general formula I.

The compounds of the claimed type are produced in conventional manner. As starting material for the synthesis there is especially employed cyanuric chloride.

If p-phenylenediamine is added as the aromatic amine component there is always first obtained the condensation product with 2 moles of cyanuric chloride, N,N'- bis(4,6 dichloro-l,3,5-triazine-2-yl)-p-phenylenediamine. The further substitution of the chlorine atom by ammonia, amines, alcohols, phenols and/or mercaptans is carried out by conventional manner.

If there is reacted with cyanuric chloride p-phenylenediamine having a substituent on one --NH group, there are always obtained condensation products which contain for one mole of triazine one mole of the substituted phenylenediamine. The further reactions on the triazine ring can be carried out by known methods.

Examples of substituted p-phenylenediamines which can be used include:

Examples of amine, alcohols, phenols and mercaptans which can be used to react with the phenylenediaminecyanuric chloride reaction product are methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, isopropylamine, butylamine, dibutylamine, sec. butylamine, di sec.butylamine, t-butylamine, methyl butyl amine, amylamine, diamylamine, 1,4-dimethylbutylamine, hexylamine, octylamine, dioctylamine, isooctylamine, decylamine, laurylamine, dilaurylamine, octadecylamine, dioctadecylarnine, ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine, allylamine, diallylamine, cyanoethylamine, cyclohexylamine, dicyclohexylamine, cyclopentylamine, cyclooctylamine, morpholine, a-naphthylamine, fi-naphthylamine, benzylamine, dibenzylamine, aniline, N-methyl aniline, N ethyl aniline, N-butyl aniline, N-amyl aniline, toluidine, piperazine, piperidine, thiomorpholine, pyrolidine, methallyl amine, methoxyethyl amine, ethoxy ethylamine, octoxypropyl amine, octadecoxyethylamine, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, t-butyl alcohol, amyl alcohol, hexyl alcohol, cyclohexyl alcohol, octyl alcohol, isooctyl alcohol, decyl alcohol, isodecyl alcohol, nonyl alcohol, dodecyl alcohol, allyl alcohol, methallyl alcohol, thiophenol, thiocresol, phenol, m-cresol, xylenol, p-ethyl phenol, p-butylphenol, p-cresol, o-cresol, p-amylphenol.

with p-phenylenediamine or the N-substituted p-phenylenediamines mentioned above.

In the following tables there are set forth representative compounds Within the invention. They can be prepared by the general procedures set forth above and more specifically can be prepared by the specific procedures set forth below:

(9.) Compounds of the general Formula III as set forth in Table 1.

9 N-benzoyl-N'-(4-monoor -dimethylamino-, -diethylamino, di-n-propylamino-, -di-ipropylaminoetc. up to -didodecylaminoas well as -diallylamino-, dimethyallylamino-, -di-cyclopentylamino-, -dicyclohexylaminoor -cyclooctylamino-6-methylthio-, -ethylthio-, -n-propylthio-, -i-propylthioetc. up to -dodecylthio-l,3,5-triazinyl-2)-pphenylenediamine, N-acetyl-, N-propionyl-, N-butyryl-, N- pentanoyletc. up to N-nonadecanoyl-N-(4-monoor -dimethylamino-, -diethylamino-, -di-n-propylamino-, -di-ipropylaminoetc. up to -di-dodecylaminoas well as -diallylamin-, -dimethallylamino-, -di-cyclopentylamin0-, -dicyclohexylaminoor -cyclooctylamino-6-methylthio-, -ethylthio-, -n-propylthio-, -i-propylthioetc. up to -dodecylthio-1,3,5-triazinyl-2)-p-phenylenediamine, N-(4-rnonoor -dimethylamino-, -diethylamino-, -di-n*propylamino-, -di-ipropylaminoetc. up to -di-dodecylamino as well as -diallylamin0-, -dirnethallylamino-, -di-cyclopentylamino-, -dicyclohexylaminoor -cyclooctylarnino-6-methylthio-, eth ylthio-, -n-propylthio-, -i-propylthioetc. up to -dodecylthio-1,3,5-triazinyl-2)-p-phenylenediamine, N-methyl-, N- ethyl-, N-i-propyl-, N-n-propyletc. up to N-octylas well as N-phenyl-N-benzyl-, N-benzoylor N-cyclohexyl-N- (4,6-dimethylthio-, -diethylthio-, -di-n-propylthi0-, -di-ipropylthioetc. up to -di-dodecylthio-1,3,5-triazinyl-2)-pphenylenediamine, N-(4,6-dimethylthio-, -diethylthio-, -din-propylthio-, -di-i-propylthioetc. up to -di-dodecylthio- 1,3,5-triazinyl-2-)-p-phenylenediamine, N-methyl-, N-ethyl-, N-i-propyl-, N-n-propyletc. up to N-octylas well as N-phenyl, N-benzyl, N-benzoyl or N-cyclohexyl-N-(4- chloro-6-methoxy-, ethoxy-, -n-propoxy-, i-propoxy-, n-butoxy-, -i-butoxyetc. up to -dodecycloxy-1,3,5-triazinyl-2)- p-phenylenediamine, N-(4-chloro-6-rnethoxy-, -ethoxy-, -npropoxy-, -i-propoxy-, -n-butoxy-, -i-butoxyetc. up to -dodecyloxy- 1,3 ,5 -triazinyl-2 -p-phenylenediamine, N-methyl-, N-ethyl-, N-i-propyl-, N-n-propyletc. up to N-octylas well as N-phenyl-, N-benzyl-, N-benzoylor N-cyclohexyl-, N'-(4-chloro-6-allyloxyor -6-rnethallyloxyor -6- cyclopentyloxyor -6-cyclohexyloxy-1,3,5-triazinyl-2)-pphenylenediamine, N-methyl-, N-ethyl-, N-i-propyl-, N-npropyl etc. up to N-octylas well as N-phenyl-, N-benzyl-, N-benzoylor N-cyclohexyl- N'-(4-methoxy-, -ethoxy-, -npropoxy-, -i-propoxy-, -n-butoxy-, -i-butoxyetc. up to -dodecyloxyas well as -allyloxy-, -metallyl0xy-, -cyclopentyloxy-, -cyclohexyloxy-, -cyclooctyloxy-6-methylthio-, -ethylthio-, -n-propylthio-, -i-propylthio-, n-butylthio-, -ibutylthioetc. up to -dodecylothio-1,3,5-triazinyl-2)-p phenylenediamine, N-methyl-, -N-ethyl-, N-i-propyl-, N-npropyletc. up to N-octyl-, as well as N-phenyl-, N-benzyl-, N-benzoylor N-cyclohexyl-, N-(4-chloro-6-morpholino-, -6-piperidino-, -6-pyrollidino-, or -6-thiamorpholinor 1,3,5-triazinyl-2)-p-phenylenediamine.

Unless otherwise indicated all parts and percentages are by weight.

Examples 16 below illustrate methods of preparation of the compounds of the invention.

Example 1 There were dissolved 369 grams of cyanuric chloride in 1500 ml. acetone and this solution was poured with strong stirring on 1000 grams of finely divided ice. There were dropped on this dispersion at C. a solution of 108 grams of p-phenylenediamine in 2 liters of acetone and subsequently a solution of 80 grams of NaOH in 200 ml. of water at the same temperature. Now the cooling medium was removed and there was added dropwise again with stirring 114 grams of allylamine and later a solution of 80 grams of NaOH in 200 ml. of water. The temperature at the end of the reaction was 45 to 50 C. After stirring for 30 minutes the mixture tested neutral, and was poured on 3 liters of water, the mixture filtered with suction, the reaction product washed with water and dried at 100 C. in a vacuum.

There resulted 433.5 grams of bis-N,N'-(4-allylamino -6-chlor0-1,3,5-triazin -2-yl)-p-phenylenediamine, a white powder having a melting point higher than 300 C. The yield was 97.5% of theory.

Example 2 444.5 grams of bis-N,N-(4-allyl-amino-6-chloro-1,3,5- triazin-2-yl)-p-phenylenediamine were introduced into a solution of 108 grams of sodium methylate in 2 liters of methanol and the mixture subsequently heated for 6 hours under reflux. The mixture then tested neutral, and was poured on 4 liters of water and the white precipitate formed was filtered with suction. The washing and drying of this precipitate took place at 80 to 90 C. in a vacuum. There was obtained the bis-N,N'-(4-allylamino-6-methoxy-1,3,5-triazin-2-yl)-p-phenylenediarnine having a melting point of 216 to 218 C. with a yield of 96.5% of theory (421.2 grams).

Example 3 There were placed in a 4 liter round flask equipped with a stirrer 2 liters of toluene and 255 grams of allyl alcohol. There were then introduced with heating in all 92 grams of sodium. The mixture was heated until the metal disappeared and then was cooled to 40 C. Then there were introduced 445 grams of solid bis-N,N-(4,6- dichloro 1,3,5-triazin-2-yl)-p-phenylenediamine and the mixture boiled at reflux until the mixture reacted neutral, was cooled somewhat, filtered and the filtrate evaporated in a vacuum. Thereby there was formed 417.1 grams of his N,N-(4,6-diallyloxy-1,3,5-triazin-2-yl)-p-pheny1enediatnine having a melting point of 330 C. and a yield of 85.3% of theory.

The bis N,N'-(4,6-dichloro-1,3,5-triazin-2-yl)-p-phenylenediamine employed in this example was prepared in the manner of example 1 prior to adding the allylamine.

Example 4 445 grams of bis-N,N'-(4-allylamine-6-chloro-1,3,5-triazin 2 yl)-p-phenylenediamine were introduced into a solution of 340 grams of sodium octyl mercaptide in 2 liters of methanol, 10 grams of trimethylamine dissolved in 100 ml. of methyl alcohol were added and the mixture stirred for 8 hours at to C. Subsequently the product was neutralized with dilute hydrochloric acid and poured into 6 liters of water. The white precipitate formed was filtered off with suction, washed and dried in a vacuum at C.

There were obtained 491.3 grams of bis-N,N'-(4-allylamino 6-octylmercapto-1,3,5-triazin-2-yl)-p-phenylenediamine having melting point of -87 C. in a yield of 91.1% of theory.

Example 5 184.5 grams of cyanuric chloride were dissolved in 1 liter of acetone and the solution poured with stirring into 1 liter of ice water. Then there was dropped in at 10 C. a solution of grams of N-phenyl-p-phenylenediamine dissolved in 800 ml. of acetone and subsequently there was added a solution of 40.1 grams of NaOH in 200 ml. of water. 9

Then there were dropped in fairly rapidly 200 grams of a 40% aqueous isopropylamine solution and the temperature allowed to rise to 45 C. The mixture quickly became neutral. The mixture was then poured into 3 liters of water, the reaction product filtered off with suction, washed with water and dried in a vacuum. The product was in the form of white crystals melting at 142 to 144 C. The yield of the N-phenyl-N'-(4-chloro-6-isopropylamino 1,3,5-triazin-2-yl)-p-phenylenediamine was 337.9 grams which was 95.3% of theory.

1 1 Example 6 354.5 grams of N-phenyl-N'-(4-chloro 6- isopropylamino-1,3,5-triazin-2-yl)-p-phenylenediamine was placed in an autoclave together with 200 grams of a 70% aqueous isopropylamine solution and 1 liter of dioxane, the autoclave closed and heated for 6 hours at 140 C. After working up as in example there were recovered 359.1 grams of N phenyl-N-(4,6-bis-isopropylamine-l,3,5-triazin-Z-yl)-p-phenylenediamine. It was in the form of white crystals having a melting point of 184 to 186 C. The yield was 82.2% of theory.

The new phenylenediamine substituted triazines can be used advantageously in the rubber processing or elastomer industry as highly effective non-discoloring or only very slightly coloring anti-ageing or fatigue protective agents.

A further purpose of the invention is the development of a process for the stabilization of vulcanized or vulcanizable rubber containing mixtures which in a given case contain fillers, which process is characterized by the inclusion of at least one 1,3,5-triazine of formula I as the stabilizing agent.

As rubbers or elastomers there can be used all crosslinkable natural and synthetic rubbers or their mixtures which can be vulcanized or cross-linked, for example, with sulfur or sulfur donors (as, for example, N,N'-dithio-bismorpholine, dipentamethylenethiuramtetrasulfide, N,N- dithiobishexahydro-ZH-azepinone-(2), and 2-benzothiazyldithio-fiI-morpholide) and known vulcanization accelerator systems, in a given case in the presence of fillers. As stated any conventional sulfur donor can be used. As examples of rubbers suitable for use in the invention there are preferably used natural rubber (NR), homo and copolymers of conjugated dienes, e.g., butadiene-styrene rubber (SBR), nitrile rubber, i.e. butadiene-acrylonitrile copolymer (NBR), polybutadiene (BR), polyisoprene (IR), polychoroprene (CR), known polymers of two olefins and in a given case a polyene hydrocarbon, especially diene hydrocarbons and trans-polypenteneamers (see Zeitschrift Kautschuk und Gummi, Kunstoffe, Vol. 23, pages 502 et seq. (1970). The invention includes the use of blends of several of the named types of rubber or elastomers.

Further butadiene copolymers which may be used in the invention are such as butadiene-acrylic acid ester copolymers, e.g. butadiene-Z-ethylhexyl acrylate copolymer, butadiene-methyl methacrylate copolymer, butadiene-vinylpyridine copolymer, butadiene alkylvinyl pyridine copolymer, e.g. butadiene-Z-vinyl-S-methylpyridine copolymer; furthermore ethylene-propylene terpolymers, e.g. ethylene-propylene-dicyclopentadiene terpolymer, ethylene-propylene-norbornadiene terpolymer, ethylene-propylene-cyclooctadiene terpolymer and ethylene-propylene-cyclododecatriene terpolymers and butyl rubber (isobutylene-butadiene copolyrner).

In a given case there can also be employed as cross linking agents for appropriate rubbers and rubber mixtures divalent metal oxides such as, for example, magnesium oxide, zinc oxide or lead oxide.

As accelerators for the vulcanization with sulfur there can be used alone or in combination known agents such as benzothiazoles (for example Z-mercaptobenzothiazole, dibenzothiazyl disulfide and the sulfenamide of Z-mercaptobenzothiazole), diphenyl guanidine, Z-mercaptoimidazoline, mercaptotriazines (for example mono and dimercaptotriazine or their sulfenamides), disulfides or polysulfides, (e.g. trisulfides and tetrasulfides), thiurams (for example tetraalkylthiuram mono or disulfides, e.g. tetramethyl thiuram monosulfide and disulfide). The thiuram accelerators are especially very suitable in those cases in which a vulcanization retarding activity occurs in order to regulate the speed of vulcanization to the desired value.

Sulfur, sulfur donors, accelerators and in a given case fillers are added to the conventional amount to the composition to be vulcanized. Thus 0.2 to 4 parts of sulfur or the equivalent amount of sulfur donor can be used. The vulcanization is carried out at customary temperatures of about to about 300 C., especially to 240 C. for customary times, e.g. 15 minutes to 2 hours, usually between 15 and 30 minutes. There can be used any of the conventional industrial processes and apparatus for this purpose, for example, heating with superheated steam, hot air, in salt baths, fluidized beds, with ultra high frequency rays and steam tubes.

The accelerators or accelerator combinations can be added together with zinc oxide and/or stearic acid.

The invention includes the use of 1,3,S-triazines of formula I for the stabilization of vulcanizates prepared from vulcanizable rubber containing mixtures. In a given case the novel stabilizers can be used in combination with known stabilizers or anti-agers. Examples of the latter materials have been set forth above.

It is further a purpose of the invention to develop a vulcanizable mixture from at least one elastomer, sulfur and/or a sulfur donor as well as at least one vulcanization accelerator or at least one oxide of a divalent metal (such as those set forth above), in a given case at least one filler and in a given case other additives known in the rubber processing industry containing at least one 1,3,5-triazine of formula I, in a given case in combination with known stabilizers or anti-ageing agent. These mixtures can be vulcanized or cross-linked and shaped.

There can be added to the starting mixtures all of the customary additives such as plasticizers, mineral oils, viscosity increasing agents, accelerators, activators such as stearic acid and in a given case zinc oxide, waxes, expanding agents, dyes, special protecting agents against ozone and pigments.

There can also be worked into the vulcanizable mixtures all kinds of blacks used in the rubber working industries as well as finely divided silica, especially silica produced in the gas phase or by precipitation from aqueous alkali metal silicate solutions, as well as silica and silicates which have been rendered hydrophobic. Additionally there can be included finely divided metal oxides including mixed oxides and mixtures of oxides; furthermore in a given case artificial and natural chalks, clays, siliceous chalk and the like can be added.

The new stabilizing agents are generally used in an amount of 0.05 to 10 parts, preferably 0.1 to 5 parts, per 100 parts by weight of polymer. The new stabilizers can be used alone or mixtures of 2 or more of them can be employed. They can also be used in combination with known antioxidants or antiagers. Such materials include, for example, phenyl-a-naphthylamine (PAN), phenyl-B- naphthylamine (PBN), N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylene diamine, N-(1,3-dimethylbutyl)-N-phenyl-p-phenylenediamine, 6 ethoxy l,2-dihydro-2,2,4-trimethylquinoline, 2,6-di-tert.- butyl-p-cresol, 4,4-dihydroxydiphenyl as well as the material set forth earlier. These adidtives can be used individually or in mixture of several of them.

When at least one compound of formula I is added to the rubber mixture, this compound acts as a stabilizer in the corresponding vulcanizate and imports a high pro tection against fatigue in dynamic stress and against ageing, especially at high temperature. Furthermore, these anti-ageing materials have the advantage not previously attained of non-discoloration of the vulcanizates produced therewith when subjected to the influence of light or provide an excellent protection against light in combination with high protection against fatigue.

These facts are illustrated in the following examples.

1 3 Example I The following vulcanizates were prepared and tested using eight different stabilizers of the invention and in comparison a known good anti-ager:

Composition Parts by weight Oil-extended styrene-butadiene rubber containing 23.5% styrene and 27.5% of highly aromatic hydrocarbon extender oil (Buna I-Iiils 1712) 96.5 Cis-polybutadiene rubber (Buma CB 30.0 HAP carbon black N 330 (Corax 3 of Degussa) 75.0

Stearic acid 1.2 Zinc oxide 4.0 Highly aromatic hydrocarbon as a plasticizer (Naftolen ZD) 15.0 Stabilizer (as set forth below) 3.0 Benzothiazyl-Z-clyclohexylsulfenamide 1.2 Sulfur 1.6

The following stabilizer of the invention were added in the amount indicated in the above formula:

p-phenylenediamine The composition was with the best known anti-aging agent based on p-phenylenediamine:

Code

IPPD N-isopropyl-N-phenyl-p-phenylenediamine Chemical Designation The comparative testing of the growth of cracks in the bend test of De Mattia was carried out after vulcanization at 160 C. to optimum cure, first without ageing. The named test of bending fatigue or crack formation of the test samples is described in the DIN (German Industrial Standards) Standard 53,522 sheet 3 and corresponds to ASTM D 813/ 1965 or the draft ISO-Recommendation N0. 173. There was measured the number of bends of the test samples which were necessary to produce a growth of the cracks formed from 4 to 8 mm. in length. The measured number of bends of the samples which contained IN stabilizers was set up in ratio to the number of bends of the test sample which contained the known antiageing agent IPPD. This ratio of the number of bends of IN per bend of IPPD was as follows:

The vulcanized test samples were aged for several days at 100 C. in a heat chest and then the above described The results Number of days of ageing at C IN 61 to IPPD. IN 58 to IPPD. IN 63 to IPPD. IN 62 to IPPD IN 59 to IPPD. IN 72 to IPPD. IN 71 to IPPD. IN 70 to IPPD."

From these figures there is evident in part the considerably superior activity of the light tested stabilizers of the invention in comparison to the previously most effective known p-phenylenediamine derivative in the rubber industry. In the unaged condition of the vulcanizate compounds IN 58, IN 59, IN 62, IN 63, IN 72, IN 71 and IN 70 already produces double or more the fatigue protection of the named IPPD. When the samples were subjected to ageing at higher temperatures, the fatigue protection remains with the effect of the IN stabilization obtained.

Example II Stabilizers IN 61, IN 58, IN 63, IN 62, IN 59, IN 72, IN 71 and IN 70 of the invention as well as IPPD were worked into the same rubber mixture as in example I and test samples produced by vulcanizing at C. as in example I. After 8 days hot air ageing of the vulcanizate at 100 C. there were produced the following changes in the measured values of tensile strength (TS) in the 200% modulus (0200) in the elongation at break (BD) in percent and the Shore-A-Hardness (SH) in points comparison to the starting values of the test samples in unaged condition:

BD SH The determinations were made according to DIN standards 53,504 and 53,505.

From the comparison values the following advantages can be recognized. By a suitable choice of stabilizer according to formula I the increase in Shore hardness under the effect of hot air can 'be reduced to above half the increase in the presence of IPPD. The simultaneous lesser increase in 200% modulus shows that the vulcanizate using the p-phenylenediamino substituted triazines has substantially less increase in hardness under the effect of heat and oxygen than in protection by IPPD. The reduction of hardening is sought at great expense in the rubber article and tire industries, since the hardening leads to a reduction in the life of the rubber articles.

Compounds according to the invention which have only one triazine ring (see formula I) likewise possess excellent properties as fatigue and age protecting agents.

In the following examples the following IN stabilizers Were tested:

N-phenyl-N- (4-chloro-6-( 1,3-dimethylbutylamino)-1,3,5-triazin-2-yl)-p-pheny1- enediamine Example HI Test samples were prepared using the receipe described in example I and employed in IN 73, IN 74, IN 75 and IN 76 in the same procedure. Tests of fatigue according to the De Mattia procedure were carried out. The following ratios of IN to IPPD were obtained without ageing:

IN 73 to IPPD 17.8-1 IN 74 to IPPD 4.4-1 IN 75 to IPPD 3.2-1

IN 76 IQ IPPD 2.9-1

After ageing of the test samples in hot air at l C. at times up to 6 days the following ratios were obtained:

Number of days of ageing IN 73 to IPPD IN 75 to IPPD. IN 76 to IPPD From these figures it can be seen that stabilizers IN 73 to IN 76 of the invention give a several fold protection against fatigue in comparison to the effect of IPPD.

Example IV Vulcanizates of the composition of example I which contained stabilizers IN 73 to IN 76 were aged for 8 days at 100 C. in hot air in the manner described in example II and the changes in physical properties determined in the same manner as in example II. The following changes Again, surprisingly the change in physical properties of the vulcanizate under the effect of heat and oxygen was less with the stabilizers of the invention than with IPPD. The new protective agents also produce an effective combination of fatigue and age resistant properties.

The fatigue and anti-ageing protective materials of the invention, however, possess in addition the great advantage that vulcanizates stabilized with them do not discolor under the action of light.

Example V There were produced vulcanizates from rubber mixtures of the following compositions which were well suited for testing for stability to light and tested for discoloration under the action of light. There were used the above described IN 61, IN 58, IN 63, IN 62 and IN 59.

Mixture number Mixture composition Parts by weight Natural rubber (first crepe) 100 100 100 100 100 100 Natural chalk 100 100 100 100 100 100 Stearie acid 1 1 1 1 1 Zinc oxide 5 5 5 5 5 5 Titanium dioxide I- 5 5 5 5 5 5 1? PD 3 IN 6L 3 IN 58- 3 IN 63---- 3 IN 62. 3 IN 59- 3 Dibenzothiszyldisulfide 1 1 1 1 1 l Tetramethylthiurammonosulfide 0. 2 0. 2 0.2 0 2 0. 2 0 2 Sulfur 2.2 2.2 2.2 2 2 2.2 2 2 The vulcanization was carried out at 150 C. for 20 minutes. The vulcanizate samples were exposed to light in a Xeno test apparatus 150, System Casella, Original Hanan (following DIN 53 388 or Draft Iso Recommendation 759). The testing of the vulcanizate samples took 16 place at room temperature at a relative atmospheric humity of 60 to The following color changes were produced in the samples at the end of the testing:

IPPD strong dark brown.

IN 61 not colored (i.e. no discoloration). IN 58 not colored.

IN 63 not colored.

IN 62 not colored.

IN 59 not colored.

It can be seen from these results that the protective agents of the present invention impart the previously unattainable combination of properties as stabilizers against growth of cracks, heat and oxygen ageing and discoloration under the effect of light.

Several of the phenylenediamine-s-triazine compounds also have proven to be efiective stabilizers against the formation of cracks under the influence of ozone.

Example VI Duration of ozone treatment (hours) 6 24 48 Norris-The significance of the code is:

0 means moderate ozone protection. means good ozone protection. means very good ozone protection.

Thus it has been shown that the triazine compounds of the invention which contain phenylendiamine groups or phenylene-diamine derivatives as ligans are novel stabilizers for rubbers which have a previously unattainable combination of activity with regard to protection against fatigue, protection against ageing, non-discoloration and, by suitable selection of substituents on the triazine ring protection against damage by ozone.

These new stabilizers can be employed with great industrial advantage in the production of carbon black containing and light colored industrial articles in all types of rubber as well as also in the production of tires for vehicles of all types.

In the following examples the following stabilizers were used as indicated.

Example VII Code Chemical Designation IN 70 N,N'-bis- 4-chloro-6-u-naphthylamino-triazinyl-2) -p-phenylenediamine IN 71 N,N'-bis-(4-chloro-6-[1,3-dimethylbutylamino] -triazinyl-2) -p-phenylenediamine IN 72 N,N bis- (4-chloro-6-isopropylamino-triazinyl- 2) -p-phenylenediamine IN 83 N,N-bis- (4-iso-propylamino-G-amino-triazinyl- 2) -p-phenylenediamine IN 93 N,N-bis- (4-allylamino-6 methylthio-triazinyl- 2 -p-phenylenediamine IN 94 N,N'-bis-(4-allylamino-6-dodecylthio-triazinyl- 2) -p-phenylenediarnine Code Chemical Designation IN 95 N,N'-bis-(4-allylamino-6-methoxy-triazinyl- 2)-p-phenylenediamine IN 96 N,N'-bis-(4-chloro-6-tert butylamino-triazinyl- 2)-p-phenylenediamine IN 114 N,N'-bis-(4-chloro-6-cyclohexylamino-triazinyl-Z)-p-phenylenediamine IN 118 N,N'-bis-(4-chloro-6-iso-propylarninotriazinyl-Z)-p-phenylenediamine IN 119 N,N'-bis-(4-allylamino-6-n-butoxy-triaziny1- 2)-p-phenylenediamine IN 121 N,N'-bis-(4-allylamino-6-[2-ethoxy-l]- triazinyl-2)-p-phenylenediamine IN 127 N,N-bis-(4-ethylamino-6-methoxytriazinyl-Z)-p-phenylenediamine IN 134 N,N'- bis-(4-[4-phenylamino-anilino]-6-methoxy-triazinyl-2)-p-phenylenediamine IN 73 N-phenyl-N-(4-chloro-6-amino-triazinyl- 2) -p-phenylenediamine IN 74 N-phenyl-N'-(4-chloro-6-allylaminotriazinyl-2) -p-phenylene diamine IN 75 N-pheny1-N-(4-chloro-6-iso-propylaminotriazinyl-2)-p-phenylenediarnine IN 76 N-phenyl-N'-(4-chloro-6-[1,3-dimethylbutylamino]-triazinyl-2)-p-phenylenediamine IN 79 N-phenyl-N-(4-chloro-6-methylthio-triazinyl- 2)-p-phenylenediamine IN 87 N-1,3-dimethylbutyl-N'-(4-chloro-6-isopropylamino-triazinyl-Z)-p-phenylenediamine IN 88 N-l,3-dimethylbutyl-N'-(4-chloro-6-allylamino-triazinyl-2)-p-phenylenediamine IN 102 N-phenyl-N'-(4-amino-6-methoxy-triazinyl- 2)-p-phenylenediamine IN 104 N-phenyl-N'-(4-amino-6-allyloxy-triazinyl- 2) -p-phenylenediamine IN 107 N-phenyl-N'-(4-amino-6-diethylaminotriazinyl-Z)-pphenylenediamine IN 108 N-pheny1-N'-(4-amino-6-allylamino-triazinyl- 2)-p-phenylenediamine IN 113 N-phenyl-N-(4-chloro-6-cyclohexylaminotriazinyl-2 -p-phenylenediamine IN 117 N-pheny1-N'-(4chloro-6-[2-hydroxy-propylamino]-triazinyl-2)-p-phenylenediamine IN 151 N-phenyl-N-(4-chloro-6-ethylamino-triazinyl- 2)-p-phenylenediamine Each of the above designated compounds was employed in the recipe described in Example I for the production of vulcanizates and these vulcanizates compared with the same recipe employing IPPD as the auti-ager.

The comparative testing was on the growth of cracks from 4 to 8 mm. long in the samples in the unaged condition and in the condition after 6 days aging at 100 C. As in Example 1 the number of bends required to produce the growth of cracks was determined and the ratio calculated.

Ratio of the number of bends (for crack growth from 4 to 8 mm.) IN to IPPD Aged 6 days Unaged at 100 0.

Compound:

From the values set forth above there can be seen the surprising effectiveness of the stabilizers of the invention in comparison to the customarily frequently employed pphenylenediamine derivatives.

Example VIII The same stabilizers of the invention as in Example VII were compared again with IPPD after working into the same rubber mixture as in Example I and producing vulcanizates at 160 C. as in Example I and testing samples in (a) the unaged condition and (b) after ageing for 6 days at C. using the same 4 tests as in Example II wherein the value recited in the table below for (a) is the actual measurement in the unaged condition and the value for (b) is the change in'this measured value after ageing measured in percent except for the Shore hardness which is measured in points.

In the right column the color determinations were made on the samples after testing in the Xeno test apparatus according to the procedure in Example V. The IPPD under the same conditions produced a very strong coloration (dark brown) in the test sample:

TS in 200 in BD in Coloring kgJcm. kgJcm. percent SH (discoloration) 33 28 32; Q8 }s1i hu colored. 153 33 610 62 D --18 +121 -41 +9 630 63 D 1%; 2; "5% *el Not colored.

175 27 690 57 D -13 +144 -40 +8 184 27 690 54 D -20 +156 -47 +9 26 725 58 D -14 +108 -34 +5 161 34 635 60 D 17 +127 47 +9 146 33 635 61 D "112 +112 at? *52 22 }S1lghtly colored.

23 is Not colored. 154 30 670 55 D 8 +167 --43 +12 169 35 615 59 D -20 +111 -41 +9 178 37 655 59 D 3 "3 "3%;

149 }Colored. 171 3 655 62 D -19 +121 45 +10 wannmconenneu TS in 200 in BD in Coloring kgJcrn. kgJemJ percent SH (discoloration) 153 34 570 61 +118 +6 }Colored. 176 34 640 59 Do l2 +115 88 +8 169 38 605 62 D 18 +190 40 +7 160 31 s90 60 DO 11 +139 46 +9 161 as s30 62 Do a; s

3%}, 3% Slightly colored. +155 +9 }Colored. 160 40 540 59 D0 32 +123 55 +9 142 37 545 63 D0 -27 +114 52 +7 147 as 540 so DO It 31 "623 it 33 iweakly colored. +100 +5 }Colored. 20 +212 57 +13 Very strongly Again there is shown in summarized fashion the superior effects of the stabilizers of the invention in the evaluation of the changes in physical properties of the vulcanizates under the influence of heat and light in comparison to IPPD. Furthermore, the anti-ageing and fatigue protective agents of the invention have a definitely better resistance to discoloration under the influence of light than IPPD. Furthermore the compounds of the invention that have groups that are symmetrically attached (for example IN 83, 93, 94, 95, etc.) produce a definite protective action against light since samples with these stabilizers showed practically no discoloration even after 6 days light treatment in the Xeno test apparatus.

Additional specific stabilizers which are suitable in the invention are N,Nbis-[4-chloro 6 4-phenylaminoanilino) -triazinyl-2-]p-phenylenediamine wherein there is the group in the 6 position of the triazine ring. This group can also be designated as 4-phenylamiuophenylamino. Similar compounds can also be used where in place of the chloro group in the 4-position there can be used Y ligands as, for example, CN, OH, OR; or --SR as f.i. compounds such as N-phenyl-N (4-cyano-6-amino-triazinyl-Z pphenylenediamine,

(4-chloro-6-amino-triazinyl 2-p-phenylenediamine,

(4-hydroxy-6-amino-triazinyl-2) p-phenylenediamine,

N-phenyl-N'- [4,6-bis- (4-phenylamino-anilino triazinyl] 2-p-phenylenediamine,

N-phcnyl-N'- [4-methoxy-6- 4'-phenylamino-anilino) triazinyl-2] p-phenylenediamine,

N-phenyl-N {4-chloro-6- (4-phenylamino-anilino triazinyl-Z -p-phenylened iamine,

N-phenyl-N [4-methylthio- (4'-phenylamino-anilino) triazinyl-2] p-phenylenediamine,

N-phenyl-N'- 4-octylthio-6- (4'-phenylamino-anilino) triazinyl-2-1p-phenylenediamine, or

N-phenyl-N'- [4-dodecylthio-6- (4'-phenylamino-anilino) triazinyl-2] p-phenylenediamine.

What is claimed is:

1. A member of the group consisting of (1) a vulcanizable elastomer composition comprising: (a) a sulfur vulcanizable polymer containing elastomer; (b) sulfur or a colored.

sulfur containing vulcanizing agent; and (c) a 1,3,5-triazine of the formula:

where Y is SR where R; is alkyl of 1 to .12 carbon atoms or aryl, CN, 0R where R is hydrogen, alkyl of 1 to 12 carbon atoms, aryl, allyl or methallyl, 4 phenylamineanilino,

where R and R are hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of l to 18 carbon atoms substituted with or 0R where R is alkyl of 1 to 8 carbon atoms, allyl, methallyl, cycloalkyl of 5 to 8 carbon atoms, aryl or benzyl, one of R and R, is alpha or beta .naphthyl with the proviso that the other is hydrogen, R and R together with the nitrogen atom form a 5 to 8 membered ring which has from 4 to 7 CH groups of which 0 or 1 hydrogen atom is substituted by lower alkyl or of which 2 hydrogen atoms attached to diiferent carbon atoms are substituted by lower alkyl, R and R together with the nitrogen atom form a 5 to 8 membered ring which has from 3 to 6 CH groups of which 0 or 1 hydrogen atom is or of which 2 hydrogen atoms attached to diflFerent carbon atoms are substituted by lower alkyl and said ring has one hetero oxygen or sulfur atom or NR where R; is hydrogen or lower alkyl, X is as defined for Y or is chlorine, Z is hydrogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl, benzyl, acyl of the formula:

where R7 is alkyl of 1 to 18 carbon atoms, benzyl or phenyl or the group as a stabilizer against heat and light, and (2) a sulfur or sulfur donor vulcanized polyene elastomer composition together with (c).

2. A composition according to claim 1 wherein X is chlorine.

3. A composition according to claim 1 wherein Z is 4. A composition according to claim 3 where X is Cl, lower alkoxy, allyloxy or alkyl mercapto and Y is where R is hydrogen, alkyl of 1 to 8 carbon atoms, hydroxy lower alkyl, lower alkoxy lower alkyl, benzyl, allyl, methallyl or phenyl, R is hydrogen, alkyl of 1 to 8 carbon atoms, hydroxy lower alkyl, naphthyl, allyl or methallyl and R and R together with the nitrogen atom are morpholino.

5. A composition according to claim 4 where X is chlorine.

6. A composition according to claim 1 where Z is hydrogen, alkyl of 1 to 8 carbon atoms, cycloalkyl of 5 to 8 carbon atoms, phenyl, benzyl, acyl of the formula 0 JLR.

where R is alkyl of 1 to 18 carbon atoms, benzyl or phenyl. I

7. A composition according to claim 6 wherein X is chlorine, lower alkoxy, allyloxy, or alkylmercapto or where R, is lower alkyl and Y is \N 12. A composition according to claim 11 where Y is where R is hydrogen, phenyl, alkyl of 1 to 8 carbon atoms,

allyl, methallyl or naphthyl and R is hydrogen or allyl.

13. A composition according to claim 10 where Z is phenyl or alkyl of 1 to 8 carbon atoms.

14. A composition according to claim 13 where Z is phenyl and Y is where R and R are hydrogen, allyl methallyl or alkyl of 1 to 8 carbon atoms.

15. A composition according to claim 14 where R, is hydrogen or allyl.

16. A composition according to claim 1 including a vulcanization accelerator.

17. A process of vulcanizing a vulcanizable elastomer composition comprising vulcanizing composition (1) of claim 1 at a temperature of to 300 C.

18. A composition according to claim 1 wherein X is chlorine and Z is N ll ax 19. A composition according to claim 1 where X is allyloxy.

20. A composition according ot claim 1 wherein at least one ofXandYis CR or and at least one of R R and R is allyl or methallyl. 21. A composition according to claim 20 wherein X is allyloxy or methallyloxy.

22. A composition according to claim 20 wherein X 18 and R is allyl or methallyl.

23. A composition according to claim 22 wherein R is allyl and R is hydrogen.

24. A composition according to claim 20 wherein Y is 4 and R is allyl or methallyl.

25. A composition according to claim 24 where R is hydrogen.

26. A composition according to claim 24 wherein R and R are both allyl.

27. A composition according to claim 24 wherein R is allyl and R is hydrogen.

References Cited UNITED STATES PATENTS 2,256,189 9/1941 Bogemann et al. 260-576 2,266,576 12/ 1941 Tuley et al. 260809 2,349,749 5/1944 Paul 260-809 3,182,072 5/1965 Ladd 260-326 3,196,180 7/1965 Albert 260-5705 3,230,219 1/ 1966 Csendes 260247.1 3,240,749 3/1966 Dexter et a1. 260-453 3,257,354 6/1966 Dexter et a1 260-45.8 3,366,598 1/1968 Westlinning et al. 26041.5

OTHER REFERENCES Gibson, Chem. Abs., vol. 64, 1966, 158890.

DONALD E. CZAJA, Primary Examiner R. A. WHITE, Assistant Examiner US. Cl. X.R.

260-458 NZ, 45.9 R, 79.5 B, 249.5, 249.8, 779, 800 

